Facilitation, complexity growth, mode coupling, and activated dynamics in supercooled liquids.
In low-temperature-supercooled liquids, below the ideal mode-coupling theory transition temperature, hopping and continuous diffusion are seen to coexist. Here, we present a theory that shows explicitly the interplay between the two processes and shows that activated hopping facilitates continuous diffusion in the otherwise frozen liquid. Several universal features arise from nonlinear interactions between the continuous diffusive dynamics described here by the mode coupling theory (MCT)] and the activated hopping (described here by the random first-order transition theory). We apply the theory to a specific system, Salol, to show that the theory correctly predicts the temperature dependence of the nonexponential stretching parameter, beta, and the primary alpha relaxation timescale, tau. The study explains why, even below the mean field ergodic to nonergodic transition, the dynamics is well described by MCT. The nonlinear coupling between the two dynamical processes modifies the relaxation behavior of the structural relaxation from what would be predicted by a theory with a complete static Gaussian barrier distribution in a manner that may be described as a facilitation effect. Furthermore, the theory correctly predicts the observed variation of the stretching exponent beta with the fragility parameter, D. These two predictions also allow the complexity growth to be predicted, in good agreement with the results of Capaccioli et al. [Capaccioli S, Ruocco G, Zamponi F (2008) J Phys Chem B 112:10652-10658].
Bhattacharyya
Sarika Maitra
SM
Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, India.
Bagchi
Biman
B
Wolynes
Peter G
PG
D003080:Cold Temperature; D004058:Diffusion; D011336:Probability; D013816:Thermodynamics